EP3673087B1 - Verfahren zum gerben von tierhaut mit dialdehyden - Google Patents

Verfahren zum gerben von tierhaut mit dialdehyden Download PDF

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Publication number
EP3673087B1
EP3673087B1 EP18773255.7A EP18773255A EP3673087B1 EP 3673087 B1 EP3673087 B1 EP 3673087B1 EP 18773255 A EP18773255 A EP 18773255A EP 3673087 B1 EP3673087 B1 EP 3673087B1
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Prior art keywords
tanning
skin
bath
dialdehyde
range
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English (en)
French (fr)
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EP3673087A1 (de
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Ramon COLOMER DURAN
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Db Patents Ltd
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Db Patents Ltd
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Priority to RS20240287A priority Critical patent/RS65388B1/sr
Publication of EP3673087A1 publication Critical patent/EP3673087A1/de
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    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/16—Chemical tanning by organic agents using aliphatic aldehydes
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/28—Multi-step processes

Definitions

  • the present invention relates to a method for tanning an animal skin.
  • the tanning method of the present invention can advantageously be used to tan an animal skin, obtaining a leather with few superficial defects (e.g. veins).
  • the tanning method according to the present invention also allows to obtain a leather with relatively high thickness and with higher superficial yields than prior art methods even starting from low weight skins.
  • the tanning method according to the invention also has a low environmental impact because it uses aldehyde tanning agents and does not require the use of chromium tanning agents.
  • luxury leather goods such as shoes, bags and garments
  • high quality leather i.e. a leather that is as free of superficial defects as possible.
  • the leather processed to produce luxury leather items must be as free of veins as possible.
  • the quality of leather depends mainly on the quality of the starting rawhide, which has to be, insofar as possible, free of defects, such as scars deriving from infections or parasites, incisions deriving from branding operations on the animals, etc.
  • the visibility of veins and stretch marks on the surface of the leather can be partially reduced in the tanning cycle, for example by adopting particular precautions in the operations of liming, dehairing or bating. Minor leather defects, moreover, can be eliminated or concealed by mechanical finishing operations (e.g. grinding, applying filler).
  • leather thickness depends mainly on the type of animal, on sex, age, and, to a lesser extent, on the characteristics of the tanning cycle applied.
  • leather of bovine origin is generally obtained with thicknesses in the 0.9 mm - 1.4 mm range.
  • leather with thickness in the 1.1 - 1.4 mm range is used for luxury leather goods.
  • Rawhides to be tanned are generally classified, based on the age of the animal, in terms of weight ranges.
  • a tanning cycle able to produce a high-thickness leather is generally characterised by a relatively low area yield.
  • a tanning cycle that produces a low-thickness leather is characterised by a relatively high area yield.
  • the area yield decreases as the weight range of the rawhide used increases.
  • the tanning cycle or process is the set of manual, mechanical and chemical-physical treatments whereby an animal hide is transformed into leather in order to preserve it or to process it further to manufacture other products.
  • the tanning cycle includes the following operating steps: a preliminary step of preparing the rawhide for tanning (beamhouse operations); an actual tanning step to make the skin imputrescible; a retanning step, in which the aesthetic and product characteristics of the tanned skin are modified as desired; a finishing step directed at improving or modifying the performance, the appearance and grain of the final leather.
  • the tanning step is carried out treating the rawhide with mineral, vegetable or synthetic (syntan) tanning agents.
  • One class of tanning agents that is highly used in the art is that of aldehydes. Aldehydes, and in particular glutaraldehyde (1,5-pentanedial), are generally used as tanning agents for rawhide pretanning. The main purpose of pre-tanning is to provide the leather with a certain degree of stability to hydrothermal treatments, so as to allow more effective fat removal treatments, at higher temperatures. Aldehyde tanning agents are also used in the retanning step to provide the final leather with more fulness and compactness, or as secondary tanning agents in chrome tanning to promote the skin tanning reaction on the part of the compounds of chromium.
  • aldehydes are a valid alternative to the use of chromium tanning agents because of their reduced environmental impact compared to the latter, aldehydes are generally not used as a single tanning agent to tan skins because they do not allow the attainment of particularly high shrinkage temperatures (Tc) (generally no higher than approximately 80°C). Moreover, tanning with aldehydes, in particularly when they are used in relatively high concentrations, can produce superficial defects in the skin (e.g. wrinkles) due to the high astringent effect of these tanning agents.
  • Tc shrinkage temperatures
  • WO 2017/009786 by the same Applicant describes an improved method for tanning an animal skin based on the treatment of the skin in a tanning bath containing a C 2 -C 8 aliphatic dialdehyde and a non-ionic surfactant.
  • the method also comprises an additional step of treating the skin in a tanning bath comprising only the aforesaid dialdehyde, in substantial absence of the aforesaid non-ionic surfactant.
  • the aforesaid tanning method allows to obtain a leather having a relatively high Tc and high mechanical resistance, without using chromium tanning agents.
  • EP1029930A1 discloses a method for tanning hides in which a hide is treated with a tanning liquor comprising a dialdehyde as the tanning agent whereby the pH value of the tanning liquor rises from an initial 2.5 - 4.0 to 5.5 or more.
  • the Applicant set out as the primary objective of providing a method for treating an animal skin that allows to overcome one or more of the drawbacks of the state of the art, illustrated above.
  • a purpose of the present invention is to provide a method for treating an animal skin that allows to obtain a leather with few superficial defects, in particular veins.
  • a second purpose of the present invention is to provide a method for treating an animal skin with which it is possible to obtain a leather with high thickness, preferably with high area yields.
  • a third purpose of the present invention is to provide a method for tanning an animal skin using aldehyde tanning agents as the sole tanning agents, which allows to prevent additional tanning treatments with non-aldehyde tanning agents, in particular chromium tanning agents.
  • the Applicant has indeed observed that by appropriately adjusting the pH at the end of a tanning treatment with aldehyde tanning agents, a tanned skin is obtained that has good hydrothermal stability and is substantially free of superficial defects, such as the wrinkles typically observable in known methods of tanning with aldehydes.
  • the skin obtained after the first stage of tanning treatment is then suitable for being subjected to one or more additional tanning treatments with aldehyde tanning agents.
  • the execution of two or more successive tanning steps with aldehyde tanning agents allows to obtain a complete cross-linking of collagen (high Tc) and, at the same time, a final leather having few superficial defects.
  • the tanning method according to the invention allows to reduce the number of superficial defects visible on the final leather, in particular in the case of leather obtained from bovine skin and, especially, from calf skins and young calf skins. The best results in terms of defect-free surface are observed on the grain side of the skin.
  • the effectiveness of the tanning treatment according to the invention is such as to make possible the production of high quality leather, with few visible superficial defects, in particular veins, even starting from low quality rawhides.
  • Skins treated with the tanning method according to the present invention do not require additional treatments with non-aldehyde tanning agents, in particular chromium tanning agents, such as pretanning, tanning and retanning treatments.
  • non-aldehyde tanning agents in particular chromium tanning agents, such as pretanning, tanning and retanning treatments.
  • the method according to the present invention moreover, allows to obtain leather with high thickness, even exceeding 1.4 mm, even starting from rawhides with low weight, and with high area yields.
  • the present invention then allows to provide high-quality leather in a simple and economical manner and with reduced environmental impact.
  • the present invention relates to a method for tanning an animal skin according to claim 1, which comprises the steps of:
  • the dialdehyde of general formula (I) is an aliphatic dialdehyde selected preferably from: glyoxal, malonic dialdehyde, succinic dialdehyde, glutardialdehyde, adipic dialdehyde and pimelic dialdehyde or mixtures thereof.
  • the dialdehyde of general formula (I) is glutardialdehyde.
  • the tanning bath can comprise one or more dialdehydes of general formula (I).
  • the total quantity of dialdehyde of general formula (I) in the tanning bath is in the range 0.1% - 30% by weight referred to the weight of the pelt, preferably in the range 0.5% - 15% by weight.
  • pellet indicates the weight of the skin in the state in which it is subjected to the first treatment with aldehyde tanning agent (step a) according to the present invention.
  • the tanning bath can also contain auxiliary tanning agents different from the dialdehyde of general formula (I). Where present, the total concentration of the auxiliary tanning agents preferably does not exceed 30% by weight referred to the weight of the pelt. Preferably, the auxiliary tanning agents do not include chromium tanning agents. Preferably, to the tanning bath are not added auxiliary tanning agents.
  • the tanning bath is substantially free of surfactants.
  • substantially free of surfactants indicates that surfactants are present in a total quantity lower than 0.05% by weight relative to the weight of the pelt.
  • the tanning bath can also comprise one or more additional surfactants, for example if skins having a relatively high fat content are treated.
  • surfactants can be anionic, cationic, non-ionic and amphiphilic.
  • any surfactants present are non-ionic surfactants, such as for example the surfactants described in WO 2017/009786 .
  • no surfactant is added to the tanning bath.
  • the tanning bath preferably has a density in the range 3-10 °Bé.
  • the density of the bath can be adjusted by addition of salts of alkaline and alkaline-earth metals, in particular sodium chloride.
  • the treatment in the tanning bath preferably has a duration of 1-7 hours, more preferably 1.5-5 hours.
  • the temperature of the tanning bath is preferably in the range 10 - 50°C, more preferably 15-40°C.
  • the quantity of tanning bath to be used can vary within a broad range in relation to the characteristics of the skin to be treated.
  • the ratio by weight in percentage terms between the tanning bath and the animal skin is in the 20% - 1000% range, more preferably in the range 50% - 600% (percentage by weight referred to the weight of the pelt).
  • the tanning bath preferably has a pH in the range 1 - 4, more preferably in the range 1.5 - 3.5.
  • the pH of the tanning bath is brought to a value above 5 and below 8 (step b); preferably the pH is brought to a value equal to or higher than 5.5 and equal to or lower than 7.5; in a particularly preferred embodiment, the pH is brought to a value equal to or higher than 6 and equal to or lower than 7.
  • Raising the pH of the tanning bath to a value in the aforesaid range allows to fix the aldehyde tanning agent to the skin in a substantially permanent manner.
  • the value of pH of the bath in step b is also called "fixing pH.”
  • the pH of the tanning bath to the fixing value can be raised with the methods known to the person skilled in the art, for example by adding to the tanning bath alkali carbonates and alkali oxides, such as sodium carbonate or bicarbonate, magnesium oxide, etc.
  • the skin is maintained in the bath at the fixing pH for a time in the range from 0.5 hours to 5 hours, more preferably from 1 hour to 3 hours.
  • the skin is subjected to at least a second treatment cycle comprising the steps a and b described above.
  • the first exhausted tanning bath can be replaced with a second fresh tanning bath having the initial characteristics of the first tanning bath, described above.
  • the treatment with the aldehyde tanning agent in the second tanning bath is then followed by raising the pH to the fixing pH value.
  • the steps a and b of the second treatment cycle are carried out with the same procedures illustrated with reference to the first treatment cycle.
  • the second treatment cycle allows to complete the cross-linking of the polypeptide chains of the collagen of the animal skin, substantially reaching the maximum shrinkage temperature Tc.
  • the Tc of the skin after the tanning treatment according to the present invention varies mainly according to the type of skin and to the specific aldehyde tanning agent used.
  • the Tc of the tanned skin is generally equal to or higher than 85°C, preferably equal to or higher than 90°C, more preferably in the range between 85°C and 95°C.
  • the skin exiting the second treatment cycle can be subjected to one or more additional treatment cycles comprising the steps a and b described above.
  • additional treatment cycles can be carried out if the Tc reached after a certain number of treatment cycles (e.g. 1 or 2 cycles) is not sufficiently high.
  • the tanning baths used in the optional treatment cycles have the same initial chemical composition of the first tanning bath and are used in the same way.
  • the steps a and b of the optional treatment cycles are carried out with the same procedures illustrated with reference to the first and second treatment cycles.
  • the skin can be optionally subjected to washing with water for the purpose, for example, of eliminating any residues or impurities that were deposited on the skin during the treatment.
  • washing is carried out in a water bath at a temperature in the 20-60°C range, more preferably in the 30 - 50°C range. Washing can be carried out once or several times. Each washing step can have a duration in the 0.5 - 4 hours range.
  • the tanning method according to the present invention can be applied to skins of different animal origin.
  • the skin is preferably selected from: bovine skin, sheep skin, goat skin and reptile skin (e.g. crocodile, snake).
  • the animal skin is a bovine skin, more preferably a calf or young calf skin.
  • the skins to be treated with the tanning method according to the present invention are unhaired skins, ready for tanning.
  • the skins can be prepared in accordance with the processes known to the person skilled in the art, subjecting them, for example, to beamhouse operations, such as: soaking, fleshing, dehairing, liming, splitting, deliming, bating, pickling and degreasing.
  • the skin to be subjected to tanning treatment according to the present invention can be previously subjected to a pickling treatment to bring the pH of the skin, for example, to a value below 4, preferably in the range of 1 to 3.
  • the pickling step can be accomplished in accordance with the techniques known in the art.
  • pickling can be carried out placing the skin in contact with a pickling bath containing an aqueous solution of sulphuric acid, possibly mixed with formic acid.
  • the pickling bath can contain salts (e.g. sodium chloride) to increase the density of the solution and prevent the skin from swelling.
  • the pickling bath has a density in the range from 3 to 15 °Bé.
  • the method according to the present invention preferably does not comprise any step of pretanning, tanning or retanning with non-aldehyde tanning agents, in particular tanning agents containing chromium.
  • the tanned and optionally washed skin may possibly be subjected to one or more subsequent finishing steps, such as a step of fatliquoring or dyeing.
  • the fatliquoring step can be carried out in accordance with the prior art.
  • the fatliquoring step can be carried out by placing the skins tanned in a bath of water comprising at least one grease and/or one fatliquor (e.g. sulphated oils) and possibly one or more surfactants.
  • fatliquoring is carried out at a temperature in the range from 20°C to 60°C, more preferably in the range from 30°C to 50°C.
  • the fatliquoring treatment preferably has a duration in the range from 0.5 to 4 hours.
  • formic acid is added to the fatliquoring bath until the pH of the bath is lowered to a value in the range from 3 to 6.
  • the tanning method according to the present invention can be carried out using the techniques and the devices that are known to the person skilled in the art.
  • the skin to be treated can be placed in contact with the aldehyde tanning agent of the tanning bath in a drum.
  • a first Dutch calf rawhide (pickled) included in a batch of weight range 11-13 was subjected to a tanning treatment in accordance with the method of the present invention.
  • the first tanning bath had the following composition (percentages by weight referred to the pelt weight of the treated skin):
  • the skin was treated in the tanning bath (step a) for 4 hours at 25°C in a drum.
  • the percentage ratio between the weight of the water of the tanning bath and the pelt weight was equal to 400%.
  • the exhausted first tanning bath was removed from the drum and replaced with a second tanning bath having the same composition as the first tanning bath.
  • the second tanning bath was used in the same weight ratio with respect to the pelt weight of the treated skin.
  • the steps a and b described above were then repeated once (second treatment cycle).
  • the tanned skin had the following characteristics:
  • the grain side of the leather had few visible superficial defects as shown in Figure 1 .
  • Example 2 A second Dutch calf raw hide included in the same batch as the skin of Example 1 was subjected to the same tanning treatment described in Example 1. For this second skin, the same results of Tc, skin thickness and area yield of the process observed in Example 1 were obtained. This demonstrates the reproducibility of the results of the process according to the previous invention.
  • the grain side of the leather had few visible superficial defects as shown in Figure 2 .
  • Example 1 By way of comparison, the Dutch calf raw hide used in Example 1 was subjected to a conventional chrome tanning treatment.
  • the grain side of the leather had a higher quantity of visible superficial defects than those of the leather of Examples 1 and 2, as shown in Figure 3 .
  • the thickness of the leather obtained with the method according to the present invention is approximately 30% greater than the thickness of the leather obtained subjecting the same raw hide to a traditional chrome tanning process.
  • the area yield of the raw hide treated with the method according to the present invention is approximately 15% greater than the area yield of the chrome tanning method.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Claims (10)

  1. Verfahren zum Gerben von Tierhaut, umfassend die folgenden Schritte:
    (a) Inkontaktbringen der Tierhaut mit einem ersten Gerbbad, das mindestens ein Dialdehyd der allgemeinen Formel (I)

            O=CH-(CH2)n-HC=O     (I)

    enthält,
    worin n 0 oder eine ganze Zahl im Bereich von 1 bis 8 ist, wobei das Gerbbad einen pH-Wert im Bereich von 1 bis 5 aufweist;
    (b) Einstellen des pH-Werts des Gerbbades auf einen pH-Wert, der höher als 5 und niedriger als 8 ist;
    (c) ein- oder mehrmaliges Wiederholen der Schritte (a) und (b) auf der aus Schritt (b) kommenden Haut unter Verwendung eines zweiten oder weiteren Gerbbades;
    wobei das erste, zweite und weitere Gerbbad im Wesentlichen frei von Tensiden ist, was bedeutet, dass Tenside in einer Gesamtmenge von weniger als 0,05 Gew.-%, bezogen auf das Blößengewicht der Haut, vorhanden sind.
  2. Verfahren nach Anspruch 1, wobei der Dialdehyd der allgemeinen Formel (I) in dem ersten und zweiten Gerbbad in einer Menge im Bereich von 0,1 Gew.-% bis 30 Gew.-%, bezogen auf das Blößengewicht der Haut, vorzugsweise im Bereich von 0,5 % bis 15 %, vorhanden ist.
  3. Verfahren nach Anspruch 1 oder 2, wobei der pH-Wert des Gerbbades in Schritt (b) auf einen Wert gleich oder höher als 5,5 und gleich und gleich oder niedriger als 7,5, vorzugsweise auf einen Wert gleich oder höher als 6 und gleich oder niedriger als 7 gebracht wird.
  4. Verfahren nach einem der vorstehenden Ansprüche, wobei der Dialdehyd der allgemeinen Formel (I) ausgewählt ist aus: Glyoxal, Malonsäuredialdehyd, Bernsteinsäuredialdehyd, Glutarsäuredialdehyd, Adipindialdehyd, Pimelaldehyd und Mischungen davon.
  5. Verfahren nach dem vorstehenden Anspruch, wobei der Dialdehyd der allgemeinen Formel (I) Glutardialdehyd ist.
  6. Verfahren nach einem der vorstehenden Ansprüche, wobei der Behandlungsschritt (a) eine Dauer im Bereich von 1 bis 7 Stunden, vorzugsweise 1,5 bis 4 Stunden, aufweist.
  7. Verfahren nach einem der vorstehenden Ansprüche, wobei das prozentuale Gewichtsverhältnis zwischen dem Gerbbad aus Schritt (a) und der Tierhaut im Bereich von 20 % bis 1000 %, vorzugsweise 50 % bis 600 %, liegt.
  8. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass es keine Gerbstoffbehandlung mit anderen Gerbstoffen als dem Dialdehyd der allgemeinen Formel (I) umfasst.
  9. Verfahren nach einem der vorstehenden Ansprüche, wobei die Tierhaut ausgewählt ist aus: Kuhhaut, Schafshaut, Ziegenhaut und Reptilienhaut.
  10. Verfahren nach dem vorstehenden Anspruch, wobei die Tierhaut eine Kuhhaut, vorzugsweise eine Kalbshaut oder eine Baby-Kalbshaut, ist.
EP18773255.7A 2017-08-23 2018-08-22 Verfahren zum gerben von tierhaut mit dialdehyden Active EP3673087B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
RS20240287A RS65388B1 (sr) 2017-08-23 2018-08-22 Postupak štavljenja životinjske kože dialdehidima

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT102017000095318A IT201700095318A1 (it) 2017-08-23 2017-08-23 Metodo per conciare una pelle animale.
PCT/IB2018/056353 WO2019038691A1 (en) 2017-08-23 2018-08-22 METHOD FOR TANNING ANIMAL SKIN WITH DIALDEHYDES

Publications (2)

Publication Number Publication Date
EP3673087A1 EP3673087A1 (de) 2020-07-01
EP3673087B1 true EP3673087B1 (de) 2023-12-13

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US (1) US20200291493A1 (de)
EP (1) EP3673087B1 (de)
JP (1) JP7461874B2 (de)
KR (1) KR102560608B1 (de)
CN (1) CN111051538B (de)
AU (1) AU2018319566B2 (de)
BR (1) BR112020003399A2 (de)
CA (1) CA3073248A1 (de)
DK (1) DK3673087T3 (de)
ES (1) ES2973419T3 (de)
IT (1) IT201700095318A1 (de)
PT (1) PT3673087T (de)
RS (1) RS65388B1 (de)
RU (1) RU2762267C2 (de)
SG (1) SG11202001411UA (de)
WO (1) WO2019038691A1 (de)

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2941859A (en) * 1959-04-08 1960-06-21 Martin L Fein Tanning with glutaraldehyde
DE4242076A1 (de) * 1992-12-14 1994-06-16 Roehm Gmbh Gerbmittel und Gerbverfahren
RU2039086C1 (ru) * 1993-04-29 1995-07-09 Научно-производственное объединение "Центральный научно-исследовательский институт кожевенно-обувной промышленности" Способ выработки кож
EP0717114A3 (de) * 1994-12-15 1996-08-21 Ciba Geigy Ag Wässrige Zusammensetzung zum Vorgerben von Hautblössen oder Nachgerben von Leder
CN1044820C (zh) * 1996-03-08 1999-08-25 徐国士 鱼皮无毒鞣制工艺
DE19906190A1 (de) * 1999-02-15 2000-08-17 Boehme Chem Fab Kg Gerbverfahren
DE10105574A1 (de) * 2001-02-06 2002-08-08 Tfl Ledertechnik Gmbh & Co Kg Kortrolliertes Verfahren zum Gerben von Häuten und Pelzen
CN101525673B (zh) * 2009-04-01 2012-06-27 陕西科技大学 一种用改性淀粉鞣剂鞣制白湿皮的工艺
CN104818354A (zh) * 2015-03-10 2015-08-05 海宁富邦汽车内饰有限公司 一种无铬鞣皮革的加工工艺
ITUB20152180A1 (it) 2015-07-14 2017-01-14 Db Patents Ltd Metodo migliorato per conciare una pelle animale.
CN105506196B (zh) * 2016-01-26 2017-11-17 湖州长城皮业有限公司 一种无铬鞣猪皮头层鞋面革制备工艺

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US20200291493A1 (en) 2020-09-17
BR112020003399A2 (pt) 2020-08-25
AU2018319566B2 (en) 2024-06-27
CN111051538B (zh) 2023-01-17
RS65388B1 (sr) 2024-04-30
KR20200049788A (ko) 2020-05-08
KR102560608B1 (ko) 2023-07-27
JP7461874B2 (ja) 2024-04-04
ES2973419T3 (es) 2024-06-20
RU2020111230A3 (de) 2021-09-24
EP3673087A1 (de) 2020-07-01
CN111051538A (zh) 2020-04-21
IT201700095318A1 (it) 2019-02-23
CA3073248A1 (en) 2019-02-28
RU2762267C2 (ru) 2021-12-17
SG11202001411UA (en) 2020-03-30
PT3673087T (pt) 2024-03-11
AU2018319566A1 (en) 2020-04-09
WO2019038691A1 (en) 2019-02-28
JP2020531637A (ja) 2020-11-05
DK3673087T3 (da) 2024-03-11
RU2020111230A (ru) 2021-09-24

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